1-carbamoyl-2-carboalkoxyamino benzimidazoles

ABSTRACT

THESE COMPOUNDS HAVE ANTHELMINTIC, ACARICIDAL, OVICIDAL AND FUNGICIDAL ACTIVITY.   (R3,R4,R5-PHENYL)-   WHEREIN R1 IS LOWER ALKYL AND R2 IS LOWER ALKYL, HALOALKYL, ALKOXY-ALKYL OR A RADICAL OF THE FORMULA   1-(R2-O-SO2-NH-CO-),2-(R1-OOC-NH-)BENZIMIDAZOLE   BENZIMIDAZOLS OF THE FORMULA

States Patent US. Cl. 266-309.: 10 Claims ABSTRACT OF THE DISCLOSUREBenzimidazols of the formula These'compounds have anthelmintic,acaricidal, ovicidal and fungicidal activity.

' The present invention relates to novel benzimidazoles of the Formula 1NHCO:R1

O: NH S 0 0 R in which R is alkyl having 1 to 4 carbon atoms, R is alkylhaving 1 to 4 carbon atoms optionally substituted by halogen or alkoxyhaving 1 to 4 carbon atoms, or a radical of the Formula 2 in whichR Rand R are hydrogen, n-alkyl of 1 to 6 carbon atoms orhalogen, or one ofR R and R is branched alkyl of 3 to 6 carbon atoms, alkoxy of 1 to 4carbon atoms, alkoxycarbonyl of 1 to 4 carbon atoms in the alkoxy group,cyano, nitro, trifluoromethyl or phenyl when the others are hydrogen. g7

Amongthe benzimidazoles of the Formula 1 those are preferred in which Ris alkyl having 1, 2, 3 or 4 carbon atoms and R is alkyl having 1 to 3carbon atoms optionally substitutedby one or several chlorine and/orfluorine atoms, or a radical of the Formula 2 in which R R and R5are'identical or different and each is hydrogen, alkyl havingrl to4;carbo n atoms, alkoxy having 1 or 2 carbon at 9 ms, carbalkoxy having1 or 2 carbon atoms, chlorine, bromine, trifluoromethyl or cyano.

The present invention also relates to a process for the manufacture ofbenzimidazole's of the Formula 1 which .7

3,772,322 Patented Nov. 13, 1973 comprises reacting acarbalkoxy-aminobenzimidazole of the Formula 3 with an alkoxyoraryloxy-sulfonyl isocyanate of the Formula 4 as follows:

To carry out the reaction the benzimidazole derivative (3) is firstsuspended in an inert solvent while stirring and the liquid or solidisocyanate (4) is added, whereupon the exothermic reaction starts. Ingeneral, the reaction product separates in the form of crystals after ashort period of time.

To complete the reaction, the reaction mixture is preferably stirred for10 to 25 hours. After that the reaction product, which is obtained in agood to very good yield, is separated from the reaction mixture byfiltration.

Suitable inert solvents to carry out the reaction are preferably thosewhich are slightly or weakly polar and have a low boiling point, forexample methylene chloride, carbon tetrachloride, benzene; others suchas diethyl ether or tetrahydrofurane; esters such as methyl acetate, andpreferably chloroform.

The carbalkoxy-aminobenzimidazoles used as starting material may beprepared by reacting the sulfate salt of a S-alkyl-pseudothiourea(obtained from dialkyl sulfate and thiourea) with two equivalents of achloroformic acid ester of the general formula ClCO R The product thusobtained reacts with ortho-phenylene diamine to yield the desiredcarbalkoxy-aminobenzimidazole (cf. J. Amer. Chem. Soc., vol. 56, p. 144(1934)).

The alkylsulfonyl isocyanates used can be prepared by the processdescribed in German Pat. 1,300,556. In this process the sulfochlorideprepared from chlorosulfonyl isocyanate and 2,4,6-trichlorophenol isreacted with the corresponding alcohols and the reaction productobtained is heated at -140 C.

The phenyloxy-sulfonyl isocyanates are prepared by the process disclosedin German Pat. 1,230,017 by heating at 120 to C. the correspondingphenols with at least 1 mol of chlorosulfonyl isocyanate inchlorobenzene.

Halogen-substituted alkoxy-sulfonyl isocyanates are obtained in the sameway by reacting the corresponding 0:- halogenated alcohols withchlorosulfonyl isocyanate.

The following sulfonyl isocyanates (4) are preferably used as startingmaterial: methoxy, ethoxy, propoxy, butoxy-, orcyclohexyloxy-sulfonylisocyanate; 2-chloroeth oxy-,2,2,2-trichloroethoxy-, 2,2,2-trifluo'roethoxy-, 2-methoxyethoxyor2-ethoxyethoxy-sulfonyl isocyanate; phe-' noxy-, 3-chlorophenoxy-,2-chlorophenoxy 2,3-dichlorophenoxy-, 2,5-dichlorophenoxy-,2,4-dichlorophenoxy- 2,6 dichlorophenoxy-4-chlorophenoxy-,3,4-dichlorophenoxy-, 3,o-dichlorophenoxy-, 2,4,5-trichlorophenoxy-, or2,4,6 trichlorophenoxy sulfonyl isocyanate; the corresponding bromoandfluoro-derivatives, as well as mixed halogen-derivatives, for example2-chloro-4-bromophenoxysulfonyl isocyanate; 2- methylphenoxy-,ii-methylphenoxy-, 4-methylphenoxy-, 2,3-, 2,4-, and2,6-dimethylphenoxy-, or 2,4,6-trimethylphenoxy-sulfonyl isocyanate; thecorresponding ethyl, propyl, isopropyl, butyl, isobu 3 tyl-, ortert.butyl derivatives, as well as the mixed derivatives.

It has also possible to use phenoxysulfonyl isocyanates containing bothhalogen and alkyl, for example, 2-chloro-6-methyl-, 2-chloro-4-methyl-,4-chloro-2-methyl-, 4- chloro-3-methyl-, 4-chloro-2,6-dimethyl-,6-chloro-2,4-dimethyl-, 2,6-dich1oro-4-methyl-, 4,6-dichloro 2 methyl-,4,6-dibromo-Z-methyl-phenoxysulfonyl isocyanate; phenoxysulfonylisocyanates substituted in 2-, 3-, 4-, and/or 6-position by cyano, nitroand/ or trifiuoromethyl groups; 2-methoxy-, 3-methoxy-, 4-methoxy-,2-ethoxy-, 4-ethoxy-, 2-carbethoxy-phenoxysulfonyl isocyanates,4-phenylphenoxyor phenylazophenoxy-sulfonyl isocyanate. Es peciallypreferred are alkoxyand phenoxysulfonyl isocyanates carrying one orseveral chlorine atoms.

The benzimidazoles according to the present invention are characterizedby a good anthelmintic effect, especially against ascarides and oxyuris.Moreover, they have an acaricidal, ovicidal and particularly afungicidal action.

They are well absorbed by the leaves and roots of plants and thus act assystemic fungicides. They can be used to combat fungus diseases ofplants either prophylactically or curatively.

The present invention therefore also relates to plant protecting agents,especially fungicides, containing as active ingredients benzimidazolesof the general Formula 1 in the usual preparations in admixture withsolid or liquid carrier substances, adhesives, wetting agents,dispersion media and grinding auxiliaries. They can be used in the formof wettable powders, emulsions, suspensions, dusts or granules. Ifdesired, they can be mixed with other fungicides with which they formcompatible mixtures.

Suitable carrier materials are mineral substances such as aluminumsilicates, argillaceous earths, kaolin, chalk, siliceous chalk, talc,kieselguhr or hydrated silicic acid, or preparations of said mineralsubstances with special additives, for example chalk with sodiumstearate. Carrier materials for liquid preparations are all suitable andcommon solvents, for example toluene, xylene, diacetone alcohol,cyclohexanone, isophorone, gasolines, paraflin oils, dioxane, dimethylformamide, dimethyl sulfoxide, ethyl acetate, tetrahydrofurance,chlorobenzene and the like.

As adhesives there can be used glutainous cellulose products orpolyvinyl alcohols.

As wetting agents there can be used all suitable emulsifiers such ashydroxyethylated alkylphenols, salts of aryl or alkylaryl-sulfonicacids, salts of oleylmethyltaurine, salts of phenyl alkyl (12-16C)-sulfonic acids or soaps.

Suitable dispersion media are salts of lignin-sulfonic acid, salts ofnaphthalene-sulfonic acid or salts of oleylmethyl-taurine.

As grinding auxiliaries suitable inorganic or organic salts can be used,for example sodium sulfate, ammonium sulfate, sodium carbonate, sodiumbicarbonate, sodium thiosulfate, sodium stearate or sodium acetate.

The following examples illustrate the invention.

(A) PREPARATION OF BENZIMIDAZOLES ACCORDING TO THE INVENTION (The Romannumerals used in this series are used in the examples of application todesignate the compound used.)

Example I 1-(2'-chloro 4 bromophenoxysulfonylcarbamoyl)-2- carbomethoxyaminobenzimidazole (I).12 parts by weight of2-carbomethoxy-aminobenzimidazole were suspended in 500 parts by volumeof absolute chloroform. 20 parts by weight of2-chloro-4-bromophenoxysulfonyl isocyanate were added while stirring.After 15 to 20 minutes the reaction mixture became distinctly brighterand the reaction product separated in the form of crystals. To completethe reaction, the reaction mixture was stirred for another 20 hours atroom temperature. The crystals were then filtered off, washed withchloroform and dried at room temperature in high vacuum. 27 parts byWeight of pure reaction product were obtained, corresponding to a yieldof of the theory. The product melted at 161- 162 C. with decomposition.

Analysis.-Calcd. for C H BrClN O S (503.5) (percent): C, 38.2; H, 2.4;N, 11.1; S, 6.4; Br, 15.9; C1, 7.1. Found (percent): C, 38.3; H, 2.4; N,11.1; S, 6.5; Br, 16.0; C1, 7.0.

The compounds listed in the following table were prepared in ananalogous manner.

Decompo- Summation formula (mol. weight), Number Chemical designationsltion, C. analysis values in percent IIl-phenoxysulfonylearbamoyl-2-carbomethoxyamlnobenzimidazole... CIGHMNOBS(390) Cale: C, 49.2; H, 3.6; N, 14.4; S, 8.2 Found: C, 49.2; H, 3.9; N,14.8; S, 8.0

III 1- -chlorophenoxysulionylcarbamoyl)-2-carbomethoxyaminobenz- 167-168C16H13C1N406s (424. 5)

lmidazole. Gale: 0, 45.3; H, 3.1; N, 13.2; S, 7 6 Found: C, 44.9; H,3.8; N, 13.1; S, 7 7

IV 1-(4-methoxyphenoxysulionylcarbamoyl)-2-earbomethoxyamino- -161 C1HUN4O S (420) benzimidazole. Cale: 48.5; H, 3.8; N, 13.3; S, 7 6 Found:C, 48.4; H, 4.4; N, 13.6; S, 7 6

V 1-(2,4-dimethylphenoxysultonylearbamoyl)-2-earbomethoxyamino- 158-159onnnmofls (418) benzimidazole.

VI 1-(2-methylphenoxysulfonylcarbamoyl)-2-carbomethoxyaminobenz- 160-162C17H1oN4OeS (404:

imidazole. Cale: N, 13.9; S, 7.9 Found: N, 13.8; S, 7.5

VII 1-(3-methylphenoxysulfonylcarbamoyl)-2-carbomethoxyamino- 161-162C17H16N406S (404) benzlmidazole. Gale: 0, 50.5; H, 4.0; N, 13.9; S, 7 9Found: C, 50.4; H, 4.2; N, 13.8; S, 8 0

VIII 1-(4'-t-butylphenoxysulfonylcarbamoyl)-2-carbomethoxyamino- 174CroHzzN40aS (447) benzimidazole. Gale: 0, 53.6; H, 5.2; N, 12.5; S, 7.2Found: C, 53.7; H, 5 0; N, 12.6; S, 6.9

IX 1(2'-eh1oro-4-methylphenoxysulfonylcarbamoyl)-2-carbomethoxy- 161-162C|1H| ClN4O S (438 5) aminobenzimidazole. Cale: N, 12.8; S, 7.3 Found:N, 12.5; S, 7.0

X 1-(2'-methyl-4,6'-dibromphenoxysulionylcarbamoyl)-2-carbo- 180-181 C1H14BrN4O S (562) methoxyaminobenzlmidazole. Cale: N, 10.0; S, 5.7 Found:N, 10.4; S, 6.0

XI 1-(2-eh1oro-6'-methylphenoxysulionylearbamoyl)-2-carb0methoxy-159-161 C 1H1 ClN4O@S (438.5)

aminobenzimidazole. Gale: 0, 46.5; H, 3.4; N, 12.8; S, 7.3 Found: C,46.0; H, 3.6; N, 12.2; S, 7.0

XII 1-(2-6-d1eh1orophenoxysulfonylcarbamoyl)-2-carbomethoxyamino-156-158 Cl6H12Cl2N40fl(459) benzimidazole. Cale: N, 12.2; S, 7.0 Found:N, 12.3; S, 6.7

TABLE-Continued Decompo- Summation formula (mol. weight), NumberChemical designation sition, analysis values in percent XL1-(3,4-dlchlorophenoxysulionylearbamoyl)-2-earbomethoxyamino- 159-162 CHizClzNlois (459) benzimidazole. Cale: C, 41.8; H, 2.6; N, 12.2; S, 7.0Found: C, 41.6; H, 2.6; N, 12.1; S, 6.9

XLI 1-(2,3-diehlorophenoxysullonylcarbamoyl)-2-carbomethoxyamino-155-157 CIQHIQCIENlOdS (459) benzimidazole. Gale: 0, 41.8; H, 2.6; N,12.2; S, 7.0 Found: C, 41.5; H, 2.7; N, 12.4; S, 6.8

XLII 1-(3,5-dich10rophenoxysulionylcarbamoyl)-2-carbomethoxyarnin0-159-160 CmHizClzILlOaS (459) benzimidazole. Cale: C, 41.8; H, 2.6; N,12.2; S, 7.0 Found: C, 41.4; H, 2.6; N, 12.4; S, 6.7

XLIII I-(2,5-dlchlor0phenoxysulfonylcarbamoyl)-2-carbomethoxyamino- 152CMHIZOIZNJOQS (459) benzimidazole. Gale: 0, 41. H, 2.6; N, 12.2; S, 7.0Found: C, 41.4; H, 2.7; N, 12.4; S, 7.0

XLIV 1-(1,3-diehloropropoxy-(2)-sulionylcarbamoyl)-2-carbomethoxy- 154C13HHC12N406S (425) aminobenzimidazole. Gale: 0, 36.7; H, 3.3; N, 13.2;S, 7.5 Found: C, 38.8; H, 3.7; N, 13.4: S, 7.6

XLV 1-(2,2,2-trlfluoroethyoxsulfonylcarbamoyl)-2-carbomethoxy- 171CnHumNlOiS (396) aminobenzimidazole.

XLVI. 1-(3-trlfiuorornethylphenoxysulionylcarbamoyl)2-carbomethoxy-149-150 C HuF N4OrS (458) aminobenzimidazole.

(B) EXAMPLES OF APPLICATION -Example 1 Cucumbers in the three-leavestage were strongly infested with conidia of cucumber mildew (Erysiphecichoracearum) and five days after the infestation the plants weredripsprayed with liquors containing decreasing amounts of the followingcompounds: XXX, XXVII, XXVI, XXXII, XXV, III, II, IV, VI, VII, and V.

As comparative agent a commercial preparation on the basis of dinocap(2,4 dinitro 6 (2 octyl)- phenylcrotonate) was used. The activeingredients were applied in concentrations of 100, 50, 25, 12, 6, 3, 1.5and 0.75 milligrams per liter of spray liquor. After drying of theliquor the plants were placed in the greenhouse and the degree ofinfestation was evaluated after two weeks.

The following Table 1 shows that the novel compounds have an excellentefliciency superior to that of the comparative substance.

TABLE 1 Efficiency in percent against Erysiphc cichora cearum with mg.of active ingredient per liter of spray-liquor of- Compound I00 25 12 63 1. 5 0. 75

Example 2 Loamy sandy soil was treated with compounds XXX, XXXII, XXVI,XXIX, and XXVIII, respectively, in amounts of 10, 5, 2.5 and 1.25milligrams of active ingredient per kilogram of soil and thoroughlymixed. As comparative agent a commercial preparation on the basis ofdinocap was used in the same amounts. The soil was filled in pots, andwheat of the type Heine VII was sown in the pots which were then placedin a greenhouse. 7 weeks after sowing when the plants had developed 6leaves they were strongly infested with conidia of powdery mildew ofcereals (Erysiphe gramz'nis), 7 days after infestation they wereexamined and the efficiency of the compounds against mildew wasascertained on a percent basis.

The results summarized in Table 2 show that the compounds of theinvention have a very good fungicidal action whereas the comparativeagent did not exhibit any action. The mode of treatment clearly showsthat the compounds of the invention were taken up by the roots and had asystemic effect.

TABLE 2 Efiieiency in percent against mildew of wheat in soil treatmentwith 111g. of active ingredient] kg. of soil of- Compound 10 5 2. 5 1.25

I00 I00 98 90 100 100 95 90 100 98 93 85 100 100 98 93 I00 90 85 80 0 00 0 Untreated 0 0 0 0 Example 3 Plants of wheat in the three-leave stagewere infested with conidia of powdery mildrew of cereals (Erysz'phegramz'lzis) and three days after infestation the plants were treatedwith preparations containing the following compounds: 11, III, XII,XIII, 1, IX, X, XXV, XVII, XXVI, IV, VIII, XXIX, XV, V, XXVIII, VI, VII,XXVII, in concentrations of 500, 250, 125, 60, 30, 15 and 7.5 milligramsof active ingredient per liter of spray liquor. As comparative agentcommercial preparation on the basis of dinocap was used in the sameconcentrations. The experiment was repeated four times.

14 days after the treatment the wheat was examined as to mildewinfestation. The results are summarized in Table 3.

Example 4 Plants of wheat were infested in the three-leave stage withconidia of powdery mildrew of cereals (Erysiphe graminis) and 6 daysafter infestation the plants were treated with preparations containingthe following compounds: II, III, XXVI, IV, VIII, XII, XXIX, XV, XIII,V, XXV, X, XVII, I, IX, XXVIII, VI, VII, XXVII, in concentrations of500, 250, 125, 60, 30 and 15 milligrams of active ingredient per literof spray liquor. As comparative agent a commercial preparation on thebasis of dinocap was used in the same concentrations. The experiment wasrepeated four times.

14 days after treatment the plants were examined as to the degree ofinfestation. The results are summarized in Table 4.

Example 5 Plants of wheat in the two-leave stage were treated with thefollowing compounds: II, III, XXVI, IV, VIII, VI, VII, XXVII, XII, XXIX,XV, XIII, V, I, IX, XXVIII, XXV, XVII, X, in concentrations of 4,000,2,000, 1,000, 500 and 250 milligrams of active ingredient per liter ofspray liquor. As comparative agent a commercial preparation on the basisof dinocap was used in the same concentrations. The experiment wasrepeated three times. After drying of the coating of active ingredientthe plants were again placed in the greenhouse and, after they haddeveloped the fifth leave, were strongly infested with conidia of mildewof cereal (Eryspihe graminis), and were then kept in a moist atmospherefor 24 hours. Subsequently they were brought again into the greenhouse.

After an incubation time of 14 days the plants were examined as to theinfestation with Erysiphe graminis. The result is listed in Table 5. Itcan be seen that all compounds of the invention had an excellentsystemic action against mildew in contrast with the comparative agent.

Example 6 Seeds of wheat were thoroughly mixed in a drum with the samecompounds as used in Example in amounts of 400, 200, 100, and 50 gramsof active ingredient per 100 kilograms of seeds. As comparative agents acommercial treating agent on the basis of mercury and a commercialpreparation on the basis of dinocap were used.

Subsequently, each time treated grains were sown, in pots in fiverepetitions, and after development of the fifth leave the plants werestrongly infested with conidia of mildew of cereals (Erysiphe graminis).After a time of incubation of 14 days the plants were examined as totheir infestation with mildrew. The result is summarized in Table 6.

Example 7 Loamy soil was mixed for 10 minutes with the compoundsindicated in Example 5 in amounts of 10, 5, 2.5 and 1.25 milligrams perkilogram of soil. As comparative agent a commercial preparation againstmildew on the basis of dinocap was used in the same amounts. Pots werefilled with the treated soil and 10 wheat grains were sown in each potin four repetitions. After germination of the wheat when they haddeveloped the fourth or fifth leave the plants were strongly infestedwith conidia of mildrew of cereals. 10 days after infestation the plantswere examined. The result is listed in Table 7.

Example 8 Cucumber plants in the two-leave stage were strongly infestedwith conidia of cucumber mildew (Erysiphe cichoracearum) andsubsequently placed in a moist atmosphere at 23 C. for 24 hours. 5 daysafter infestation, the plants were treated 3 times with the compoundsindicated in Example 5 in amounts of 100, 59, 25, 12, 6 and 3 milligramsof active ingredient per liter of spray liquor. As comparative agent acommercial preparation on the basis of dinocap was used. After drying ofthe spray liquor the plants were placed in the greenhouse, and after anincubation time of 14 days, were examined as to the degree of mildew.The results are listed in Table 8.

TABLE 3 Efiicieney in percent against powdery mildew of wheat with mg.of active ingredient per liter of spray liquor of Compound 500 250 12060 30 100 100 97 95 90 90 85 Comparative agen 100 85 70 60 35 0 0Untreated TABLE 4 Efficiency in percent against powdery mildew of wheatwith mg. of active ingredient p r liter of spray liquor of- 5 Compound500 250 120 66 3O II 97 95 9O 85 65 40 III. 100 97 97 95 90 65 XXVI 9795 90 85 65 40 1V.-. 97 95 90 85 65 40 VIII 97 95 90 85 75 40 1O XII 10097 95 85 65 0 XXIX 100 97 97 90 90 75 XV-.. 100 97 95 85 65 0 XIII 100100 97 95 90 65 XXV. 100 100 100 97 95 90 XVII. 100 97 95 85 75 65XXVIIL- 97 97 95 90 65 40 VII... 97 95 9O 90 75 40 XXVII 100 97 95 90 9085 Comparative agent- 85 70 55 30 0 O 20 Untreated 0 0 0 0 O 0 TABLE 5Eifieieney in percent against powdery mildew of wheat with mg. of activeingredient per liter of spray liquor of Compound 4, 000 2, 000 1, 000500 250 100 97 95 90 65 109 97 95 90 75 97 95 85 75 65 100 97 95 90 65100 97 95 90 65 V 190 95 90 85 65 VII 100 95 90 75 XXVII 100 95 90 85 65XII 100 100 97 95 90 4O XXIX 100 97 97 95 85 XV 100 97 90 85 65 XIII 100100 97 97 9 0 V 100 97 90 85 65 I 10D 97 95 90 85 IX 100 97 95 85 65XXVIII 100 95 90 85 65 V 100 100 97 9O 85 109 100 97 97 9O 100 100 97 9590 Comparative agent. 0 0 0 0 0 Untreated 0 0 0 0 0 TABLE 6 Eflieiencyin percent against mildew in wheat after seed treatment with grams ofactive ingredient per 100 kg. of seed oi Compound 400 200 100 53 100 9585 40 97 90 85 85 65 0 100 95 90 65 97 95 90 75 100 97 90 4O 98 97 90 6595 90 75 0 100 95 90 100 95 85 75 97 95 85 75 100 97 95 97 85 0 97 95 9085 95 90 85 75 95 9O 75 O 97 95 90 75 100 97 85 97 95 85 75 Comparativeagent. 0 0 0 0 Comparative agent... 0 0 0 0 Untreated 0 0 0 0 TABLE 7TABLE 9 Eiliciency in percent against mildew in wheat Efliciency againstcucumber mildew in percent insoiltreatmentwith mg. of active ingredientwith mg. of active ingredient per liter of per kg. of soil ofsprayliquor of-- Compound 10 2. 5 1. 25 5 Compound 1, 000 500 250 125 199 9795 85 99 85 75 65 199 97 95 85 97 95 85 75 100 97 95 65 75 40 0 0 100 9790 85 97 95 85 65 95 90 85 75 75 65 0 9 100 97 97 99 90 85 75 65 109 10095 85 97 95 99 85 100 97 99 65 85 75 40 0 199 97 95 95 97 95 75 69 19997 90 65 75 65 0 0 109 97 99 75 199 95 75 60 199 190 97 85 109 95 85 70100 97 95 85 75 65 49 0 109 97 95 75 97 90 75 60 109 97 95 75 97 95 7565 97 95 85 75 99 85 75 40 109 97 97 90 97 95 85 65 109 97 97 95 109 9790 75 199 97 95 85 97 85 65 0 Comparative agent..." 0 0 0 0 ve 0 0 0 0Untreated 0 0 0 0 20 Untreated 0 0 0 0 TABLE TABLE 8 Efficiency inpercent against cucumber mildew with mg. of active ingredient per literof Efilcrcncy 1n percent against cucumber nuldew spray liquor ofwith mg.of active ingredient per liter of spray hquor Compound 200 109 59Compound 100 25 12 6 85 0 0 95 85 65 0 100 97 97 95 99 65 40 0 0 190 19997 97 90 95 95 65 o 109 97 97 90 85 95 99 65 109 199 97 90 o 75 65 0 100100 97 95 85 99 85 65 0 100 97 95 s5 85 75 65 0 190 100 199 97 95 99 8575 190 97 95 90 65 75 65 0 0 190 109 190 97 95 97 90 75 49 190 97 95 907 95 90 85 109 199 97 97 95 95 99 65 0 109 190 109 100 95 97 95 90 75109 100 97 95 90 99 85 75 75 100 100 97 95 90 75 65 49 0 199 100 97 9599 109 97 90 75 199 97 99 75 40 109 97 95 90 100 190 100 97 95 90 85 7565 X 199 igg 199 97 9 5 0 o 0 0 190 9 95 9 s0 0 o 0 0 Comparativeagent-.." 109 99 75 60 30 0 Untreatod Untreated O 0 0 O 0 0 Example 11Loamy soil was thoroughly mixed for 10 minutes with E mpl 9 thecompounds indicated in Example 5 in amounts of Cucumber plants in thetwo-leave stage were treated and mlnlgmmslper ii f f t gz with thecompounds indicated in Example 5 in amounts z P agent g fifi 9 3 framedof 1000, 500, 250 and milligrams per liter of spray 5O mocapbwas o s i e5 etitions liquor. After drying of the coating, the plants were broughter See 3 f if? m e s 1n z the into a greenhouse. After the plants thustreated had develan polts i g q thg Ware oped the fifth or sixth leavethey were strongly infested cucuml 2 g; eve P f elf b f g kc t withconidia of cucumber mildew (Erysiphe cichoracei W1 a o bro i arum), keptin a moist atmosphere and, after 24 hours Ours m a mols a em g 00 intothe greenhouse. After a t1me of incubation of 14 were brought again intothe greenhouse. After an incubation time of 14 days the plants wereexamined as to the degree of mildew. The result is listed in Table 9.

Example 10 Plants of cucumbers having 2 leaves were treated on the lowerside of the leaves only with the compounds indicated in Example 5, whilecare was taken that no active ingredient came into contact with theupper sides. The compounds were used in amounts of 200, 100, 50 and 25milligrams of active ingredient per liter of spray liquor. Ascomparative agent a commercial preparation on the basis of dinocap wasused in the same concentration.

After drying of the coating the untreated upper sides of the leaves werecautiously infested with conidia of encumber mildew and the plants wereplaced in a moist atmosphere. After 24 hours the plants were broughtinto the greenhouse and 14 days later they were examined as to thedegree of infestation with mildew. The result is listed in Table 10.

days, the cucumber plants were examined as to the degree of infestationwith mildew. The result is summarized in Table 11.

Example 12 Cucumber seeds were thoroughly mixed for 10 minutes in a drumwith the compounds indicated in Example 5 in amounts of 400, 200, 100and 50 grams of active ingredient per 100 kilograms of seeds. Ascomparative agent two commercial preparations, one on the basis ofmercury and the other on the basis of dinocap, were used in the sameamounts, but calculated on the preparations. The treated seeds were sownin pots in 5 repetitions. When the plants had developed their fifth leafthey were strongly infested with conidia of cucumber mildew and placedat once in a moist atmosphere of 23 C. After a residence time of 24hours the plants were brought into a greenhouse where they were examinedafter 14 days as to the degree of infestation with mildew. The result isindicated in Table 12.

r TABLE 11 14 in the greenhouse where they were examined after anincubation time of 21 days as to their degree of infestation withCercospora bericola. The result is indicated in Table 14.

Compound 5 2.5 1.25 5 TABLE 13 100 100 97 75 Eiiiciency in percentagainst Oercospora 100 100 97 75 beticola in sugar beet with mg. ofactive 100 100 97 85 ingredient per liter of spray liquor of- 100 100 9795 100 I00 97 90 Compound 25 12 6 3 1. 5 100 97 95 75 100 100 97 85 100100 97 90 80 100 100 95 75 100 100 97 95 80 100 100 97 95 100 97 95 9075 100 100 97 97 100 97 95 90 7 0 100 97 95 85 100 97 95 90 85 100 100100 95 100 97 95 85 75 100 i 100 95 75 100 97 95 85 70 100 100 97 90 100100 97 90 85 100 I00 97 90 100 100 97 97 90 100 97 95 85 100 100 97 9790 100 100 97 97 100 97 95 95 90 100 100 97 95 100 100 100 97 90 X r 100100 97 85 100 97 95 90 80 Comparative agent 0 0 0 0 100 97 97 95 90Untreated; 0 0 0 0 100 97 97 95 90 100 100 97 95 85 100 100 100 97 90100 100 100 97 90 100 97 95 95 90 Comparative agent, copperCOXlOhlOILidG "I; 75 38 0 0 0 ompara ive agent, mane 90 65 40 25 0 TA E12 25 Untreated o 0 0 o o Efficiency against cucumber mildew in per centin seed treatment with mg. of active ingredient per 100 kg. of seeds of-TABLE 14 Compound 400 200 100 Efiiciency in percent against Cercospom II100 97 95 85 3O beticola in sugar beet with mg. of active III. 100 97 9085 ingredient per liter of spray liquor XXV 95 85 75 IV 100 97 90 85Compound 250 120 60 30 VIII 100 97 90 75 VI. 97 97 90 85 100 97 95 85VII 97 95 90 75 100 100 97 95 XXVII... 97 95 90 40 100 97 95 90 II 97 9590 100 97 95 90 XXIX.. 97 95 90 85 100 95 85 65 V 95 90 85 S0 100 97 9585 XIIL 100 95 90 100 97 95 75 V 97 95 90 75 100 97 90 85 I1. 97 95 8565 100 97 95 85 IX v 97 95 90 75 100 97 95 85 XXVIII..-. 97 95 75 65 10097 95 85 XXV..- 100 97 90 75 100 100 97 95 XVII 95 90 70 100 97 65 X 9795 75 100 97 85 Comparative agent- 0 0 0 0 97 95 90 85 Comparativeagent. 0 0 0 0 100 97 95 85 Untreated 0 0 0 0 100 100 97 95 100 100 9795 100 97 95 85 Comparative agent, copper oxichloride 45 20 0 0Comparative agent, maneb. 60 30 0 0 Untreated O 0 0 0 Example 13 50Sugar beet plants were treated w1th the compounds m 1 15 indlcated 1nExample 5 in amounts of 25, 12.5, 6 and 3 a p e milligrams of activeingredient per liter of spray liquor. As comparative agents commercialpreparations on the basis of copper oxichloride and on the basis ofmaneb (manganese (ethylene-bis-dithiocarbamate)) were used. After dryingof the coating, the plants were strongly infested with spores ofCercospora beticola and then placed in a moist atmosphere of 25 C. Aftera residence time of, 24 hours, the plants were brought into thegreenhouse and examined after an incubation time of 21 days as to thedegree of infestation with Cercospora beticola. The result is listed inTable 13.

Example 14 Sugar beet plants were strongly infested with spores ofCert-ospora beticola and placed at once in a moist atmosphere of 25 C.After 24 hours the plants were transferred into the greenhouse. 6 daysafter infestation the plants were treated with the compounds indicatedin Example 5 in concentrations'of 250, 120, 60 and 30 milligrams ofactive ingredient per liter of spray liquor. As comparative agentspreparations on the basis of copper oxichloride and maneb were'used.After drying of the coating of active ingredient the plants were placedagain Apple seedlings in the 4-leave stage were artificially infested inthe usual manner with conidia of a'pply mildew (Podosphaera leucotricha)and 5 days after infestation the seedlings were treated with thefollowing compounds: II, III, XXVI, IV, VIII, VI, VII, XXVII, XII, XXIX,XV, XIII, V, I, IX, XXVIII, XXV, XVII, X, XXX, XXXI, XXXI-I, inconcentrations of 59, 25, 12, 6 and 3 milligrams of active ingredientper liter of spray liquor. As comparative agent a commercial preparationon the basis of binapacryl (2-sek-buty1 4,6 dinitrophenyl-3-methyl-butenoate) Was used with the same concentration of activeingredient. The experiment Was repeated 4 times.

After an incubation time of 14 days the plants Were examined as to thedegree of infestation with apple mildew. The result is indicated inTable 15.

Example 16 Tomato plants of the type Rheinlands Ruhm in the grown-upthree leave stage were treated with the compounds indicated in Example15 in concentrations of 100, 50, 25, 12 and 6 milligrams of activeingredient per liter of spray liquor. As comparative agent maneb wasused in the same concentrations.

TABLE Etfieieney in percent against apple mildew with mg. of activeingredient per liter of spray liquor of Compound 50 12 6 3 100 109 97 9795 199 199 100 97 95 97 99 85 49 199 100 190 97 95 95 90 75 60 109 10997 97 95 100 199 100 97 95 190 199 97 95 99 100 97 95 90 85 199 109 9790 65 109 100 97 95 99 100 100 100 97 95 100 190 190 97 99 100 199 19095 90 100 97 95 90 85 97 95 99 85 75 109 190 199 97 97 100 100 97 97 9597 95 90 85 70 109 100 100 97 95 199 97 95 90 95 199 190 199 97 97Comparative agent. 90 85 60 40 0 Untreated 0 0 0 O 0 TABLE 16 Eflicieneyin percent against Cladosporium jolt-um on tomato plants with mg ofactive ingredient per liter of spray liquor of- Compound 100 25 12 6 190100 97 95 90 190 100 97 95 90 100 97 97 95 85 100 199 97 95 99 199 19990 85 89 190 109 97 90 75 100 100 97 90 90 190 199 97 95 85 190 95 90 7570 100 199 97 97 90 199 109 95 90 75 109 97 99 85 75 199 109 97 95 85199 109 95 99 85 199 95 95 90 80 100 109 97 99 85 109 109 190 95 95 100190 95 90 75 199 90 85 75 70 109 199 190 95 85 199 199 95 90 80 II 109109 199 97 95 Comparative agent 95 70 59 25 0 Untreated 0 9 0 0 9Example 17 Tomato plants of the type Rheinlands Ruhm in the grown upthree-leave stage were strongly infested with conidia of Cladosporiumfulvum, kept for 24 hours in a moist atmosphere and then placed in agreenhouse. 5 days after infestation the plants were treated with thecompounds indicated in Example 15 and, after drying of the spray liquor,were again brought into the greenhouse. The active ingredients were usedin concentrations of 259, 120, 60, 30, and 15 milligrams per liter ofspray liquor. As comparative agent a commercial preparation on the basisof zineb (zinc ethylene bisdithiocarbamate) was used in the sameconcentration of active ingredient.

3 Weeks after treatment the plants were examined as to the degree ofinfestation with Cladosporium fulvum. The result is summarized in Table17.

Example 18 Celery plants of the type Magde'burger Markt were treated inthe four-leave stage with the compounds in- 16 dicated in Example 15 inconcentrations of 500, 250, 120, and 69 milligrams of active ingredientper liter of spray liquor. As comparative agents commercial preparationson the basis of copper oxichloride and on the basis of maneb were usedin the same concentrations.

One day after drying of the spray liquor the plants were stronglyinfested in the usual manner with spores of Septoria apii, placed for 24hours in a moist atmosphere of 25 C. and then brought into a greenhouse.3 weeks after infestation the plants were examined. The result isindicated in Table 18.

TABLE 17 Elfieiency in percent against Cladosporium falqum on tomatoplants with mg. of aetlve ingredient per liter of spray liquor Compound250 120 60 3O 15 III 199 97 99 85 75 Comparative agent. 70 30 0 0 0Untreated 0 0 0 0 0 TABLE 18 Efiieieney in percent against Szptorialapii on celery with mg. of active ingredient per liter of spray liquorof- Compound 500 250 60 Comparative agent, maneb. 70 45 20 9 Comparativeagent, copper oxiehloride 60 30 r 0 Untreated 0 0 0 0 Example 19 Riceplants in the three-leave stage were treated with the compounds of theinvention indicated in Example 15 in concentrations of 509, 250, 129,60, and 39 milligrams per liter of spray liquor. As comparative agent acommercial preparation on the basis of maneb was used in the sameconcentrations. After drying of the spray liquor, the plants werestrongly infested with spores of Piricularia oryzae, placed in a moistatmosphere of 25 C. and then brought into a greenhouse. Two weeks afterinfestation, the plants were examined as to the degree of disease. Theresult is summarized in Table 19.

1 17 7 Example 20 Kidney beans were thoroughly mixed for 10 minutes in adrum with the following compounds of the invention inlconcentrations'of200, 100, 50, 25, and 12.5 grams of active ingredient per 100 kilogramsof beans: II, III, XXVI, IV, VIII, VI, VII, XXVII,, XII, XXIX, XV, XIII,V, I, IX, XXVIII, XXV, XVII, X, XXX, XXXI, XXXILXIX, XVI, XIV. Ascomparative agent a preparation on the basis of pentachloronitrobenzenewas used in the same concentrations. The experiment was repeated 4times. One day after the treatment equal numbers of beans were sown inpots in a soil strongly infested with Rhizoctonz'a so lani and the potswere placed in the greenhouse.

3 weeks after germination the healthy plants were counted. The result isindicated in Table 20.

TABLE 19 Efilciency in percent against Piricularia 20 oryzae on ricewith mg. of active ingredient per liter of spray liquor of- Compound 500250 120 60 so 100 95 9o 65 50 100 95 9o 65 5o 100 95 9o 85 75 100 100 9795 85 95 9o 85 7o 65 100 97 95 9o 35 100 97 95 9o 85 95 9o 75 65 50 959o 70 65 55 95 90 so 70 55 100 97 90 85 75 100 97 95 so so 100 100 97 9590 97 90 85 70 65 95 85 75 65 50 95 85 so 70 60 100 100 97 95 9o 100 9790 e5 65 95 9o 85 65 50 100 100 97 90 85 97 90 85 7o 65 100 97 95 90 85Comparative agent. 70 45 0 0 0 Untreated 0 0 0 0 0 TABLE 20 Efiieiencyin percent against Rhizoctonia solrmi in dwarf beans after seedtreatment with g. of active ingredient per 100 kg. of seed of- Compound200 100 25 12.5

100 90 90 so 70 100 100 95 90 so 50 100 100 100 90 so 100 100 90 so 70100 90 so 70 100 100 95 90 so 100 95 90 so 75 100 100 100 90 s5 100 959o 85 7o 55 100 100 95 9o 85 100 9o 85 75 100 100 90 so 70 100 9o 85 so70 100 95 90 so 100 95 so 75 60 100 90 s5 70 55 100 100 100 95 90 0 10090 7o 65 100 9o 85 7o 65 100 100 9o 85 75 100 85 7o 65 100 100 100 so 959o 85 75 mo 95 85 7o 65 65 100 90 so 65 6o tive ag 90 60 45 30 0Untreated..- 0 0 0 0 0 Example 21 70 A wettable powder containing1-(2-chloro-4-bromophenoxysulfonylcarbamoyl) 2carbomethoxy-ammobenzimidazole(I) as active ingredient was prepared bymixing 75 20% by weight of active ingredient 13% by weight of highlydisperse silicic acid (Silcasil Z) 49% by weight of magnesium-aluminumsilicate (Sillitin Z) 10% by weight of sulfite waste liquor 1% by weightof oleic acid methyl tauride (Hostapon T) 7% by weight of wetting agentPreparations of the other compounds were made in an analogous manner.

Example 22 Albino rats were orally infested each with 1,000 eggs ofHeterakis spumosa. After termination of the prepatent period (about 7weeks), the active ingredients were administered once p.o. or s.c. Theresults were evaluated one week after administration. For this purposethe animals were killed, dissected and the living and dead parasiteswere counted.

The results are summarized in the following Table 21.

TABLE 21 Administration against Tolerated rnax- Heterakis spumosa withEfiiciency, imum dose in mg. of active ingredient percent of mgJkg. ofper kg. of body weight s.c. dead paramouse (5.0. and Compound and p.o.sites p.o.)

XXV 1 x 200 5.0 100 800 5.0.

1 x 200 p.o 100 800 p.oz

XLIII 1 x 1,000 s.c 100 800 so.

1 x 1,000 p.o 100 1,600 p.o.

XXX 1 x 100 so 100 200 so.

1 x no 100 200 11.0;

XLI 1 x 300 so 100 400 5.0.

1 x 600 p.o 100 1,600 p.o.

XLII l x 300 s.c 100 400 so.

1 x 200 p.o 100 800 p.o.

XLIV 1 x 150 so 100 200 s.c.

1 x 400 p.o- 100 800 p.o.

XXXIV 1x300 5.0.. 100 400 5.0.

1 x 600 p.o 100 800 p.o.

We claim:

1. Benzimidazole of the formula in which R is alkyl of 1 to 4 carbonatoms, R is alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atomssubstituted by halogen or by alkoxy of 1 to 4 carbon atoms, or a radicalof the formula in which R R and R are hydrogen, n-alkyl of 1 to 6 carbonatoms or halogen, or one of R R and R is branched alkyl of 3 to 6 carbonatoms, alkoxy of 1 to 4 carbon atoms; alkoxycarbonyl of l to 4 carbonatoms in the alkoxy group, cyano, nitro, trifluoromethyl or phenyl whenthe others are hydrogen.

2. 1-(2,4'-dichlorophenoxysulfonyl carbamoyl) 2-carbomethoxy-aminobenzimidazole.

3. 1-(3-chlorophenoxysulfonylcarbamoyl) 2carbomethoxy-aminobenzimidazole.

